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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
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Solution aggregation of platinum(ii) triimine methyl complexes.

Vikas M Shingade1, William B Connick1

  • 1Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221-0172, USA. vikas.shingade@gmail.com.

Dalton Transactions (Cambridge, England : 2003)
|July 30, 2020
PubMed
Summary

Two platinum complexes, [Pt(tpy)(CH3)](PF6) and [Pt(mbzimpy)(CH3)](PF6), form dimers in solution. The [Pt(mbzimpy)(CH3)](PF6) complex shows a greater tendency to aggregate, forming head-to-tail molecular arrangements.

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Area of Science:

  • Organometallic Chemistry
  • Supramolecular Chemistry
  • Nuclear Magnetic Resonance (NMR) Spectroscopy

Background:

  • Platinum complexes with terpyridine ligands are of interest in various chemical applications.
  • Understanding self-assembly and aggregation behavior in solution is crucial for designing functional molecules.
  • NMR spectroscopy is a powerful tool for characterizing molecular structure and interactions in solution.

Purpose of the Study:

  • To investigate the solution-phase aggregation behavior of two platinum complexes: [Pt(tpy)(CH3)](PF6) and [Pt(mbzimpy)(CH3)](PF6).
  • To quantify the dimerization tendency of these complexes using NMR chemical shift data.
  • To elucidate the structural arrangement of the observed dimers.

Main Methods:

  • Nuclear Magnetic Resonance (NMR) spectroscopy, specifically monitoring chemical shifts in DMSO-d6.
  • Concentration-dependent NMR studies to observe aggregation phenomena.
  • Two-dimensional proton-proton Nuclear Overhauser Effect SpectroscopY (2D 1H-1H NOESY) to determine dimer conformation.

Main Results:

  • Both platinum complexes, [Pt(tpy)(CH3)](PF6) (1) and [Pt(mbzimpy)(CH3)](PF6) (2), exhibited concentration-dependent NMR chemical shifts, indicating dimer formation.
  • Equilibrium constants (K) revealed that complex 2 ([Pt(mbzimpy)(CH3)](PF6)) has a significantly higher propensity for aggregation in solution compared to complex 1.
  • 2D 1H-1H NOESY experiments confirmed a head-to-tail molecular stacking arrangement within the dimers of both complexes.

Conclusions:

  • The study demonstrates that platinum complexes with terpyridine-based ligands can undergo concentration-dependent dimerization in solution.
  • The N-methylbenzimidazolylpyridine ligand in complex 2 promotes stronger intermolecular interactions and aggregation.
  • The head-to-tail stacking motif is the preferred structural conformation for these platinum complex dimers in solution.